Spray-dried granules of high apparent density

ABSTRACT

The process of producing spray-dried granules useful as detergents, cleaning compositions, or as a component therefor, by preparing a slurry containing 0.2% to 20% by weight of sugar acids or salts thereof and the balance being detergent components, wherein the slurry contains less than 35% by weight of water and has a viscosity of less than 15,000 mPas under spray-drying conditions, and spray-drying the slurry.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to spray-dried granules which are particularlysuitable for use as detergents or cleaning compositions or for use indetergents or cleaning compositions and which have an apparent densityof at least 700 g/l and to a spray-drying process for the production ofthese heavy granules.

It is generally known that, depending on the formulation, apparentdensities of around 600 to 650 g/l can be obtained by conventional spraydrying in which inflated, i.e. porous, granules are generally formed. Afurther increase in apparent density can be obtained either by sprayingthese porous granules with nonionic surfactants, in which case the poresof the granules are filled, or by powdering them with fine-particlepowders, for example zeolite powders.

2. Discussion of Related Art

European patent application EP-A-0 120 492 describes special spray-driedgranules which even reach an apparent density of at least 550 g/l to 800g/l without the above-described aftertreatment. These granules containethoxylated alcohols containing 12 to 24 carbon atoms and an average of3 to 20 ethylene oxide groups. To achieve an apparent density as high asthis, it is essential that the content of anionic surfactants in thesegranules should be less than 1% by weight and the soap content less than0.2% by weight because small quantities of such additives lead duringspray drying to inflation of the granules and hence to a reduction inthe desired high apparent density and to a deterioration in the flowproperties of the granules. The granules are produced by a process inwhich a slurry containing 55 to 35% by weight of water (including thewater bound by adsorption or as hydrate) is sprayed. However, the watercontent is preferably no lower than 42% by weight because lower contentslead to a significant increase in the viscosity of the slurry andnecessitate the addition of viscosity-reducing agents, such as toluene,xylene or cumene sulfonate. Slurry viscosities of up to at most 15,000mPas under operating conditions are regarded as acceptable.

The problem addressed by the present invention was to make the spraydrying process more favorable from the energy point of view and toobtain an increase in the performance of the spray drying towers andhence an increase in the capacity of existing installations for the sameenergy consumption. To this end, it should be possible to spray slurriesof higher concentration. However, these slurries should not have suchhigh viscosities that they can no longer be sprayed. In addition, therewould be no need for additives, such as toluene, xylene or cumenesulfonate, as typical viscosity-reducing agents.

DESCRIPTION OF THE INVENTION

It has now been found that slurries of relatively high concentration canbe sprayed in conventional spray drying towers if they contain certainadditional substances which are already known ingredients of detergentsor cleaning compositions where they are used in particular asco-builders.

In a first embodiment, therefore, the present invention relates tospray-dried granules which may be used in particular as detergents orcleaning compositions or as a component therefor, contain nonionicsurfactants in the quantities mentioned below, but anionic surfactantsin quantities of less than 1% by weight and soap in quantities of lessthan 0.2% by weight and have an apparent density of at least 550 g/l,the granules containing 1 to 30% by weight of nonionic surfactants and,in addition, sugar acids or salts of sugar acids.

Preferred granules have an apparent density of at least 600 g/l,preferably 700 to 1000 g/l and, more preferably, around 750 to 800 g/l.In the context of the present invention, spray-dried granules of highapparent density, more particularly with apparent densities of at least700 g/l, are produced exclusively by a spray drying process.Aftertreatments, such as impregnation with liquid to wax-likecomponents, for example nonionic surfactants, powdering withfine-particle powders or the use of the granules in mixing and/orgranulation or extrusion processes optionally having an even greatercompacting effect, are by no means ruled out, but are not essential tothe invention. Accordingly, the apparent density data always relate tothe basic granules obtained by spray drying.

Granules according to the present invention are substantially free fromtypical anionic surfactants and soaps. Their anionic surfactant contentis less than 1% by weight while their soap content is less than 0.2% byweight. Preferred spray-dried granules are even completely free fromanionic surfactants and/or soaps.

By contrast, the nonionic surfactant content of the granules ispreferably from 2 to 25% by weight and, more preferably, from 5 to 20%by weight. Preferred nonionic surfactants are alkoxylated,advantageously liquid ethoxylated, more especially primary alcoholspreferably containing 8 to 24 carbon atoms and, more particularly, 8 to18 carbon atoms and an average of 1 to 80 moles of ethylene oxide (EO)per mole of alcohol, in which the alcohol radical may be linear or,preferably, 2-methyl-branched or may contain the mixtures of linear andmethyl-branched radicals typically present in oxoalcohol radicals.However, alcohol ethoxylates containing linear radicals of alcohols ofnative origin with 12 to 18 carbon atoms, for example coconut oil, palmkernel oil, tallow fatty or oleyl alcohol, and an average of 2 to 8 EOper mole of alcohol are particularly preferred. Preferred ethoxylatedalcohols include, for example, C₁₂₋₁₄ alcohols containing 3 EO or 4 EO,C₉₋₁₁ alcohol containing 7 EO, C₁₃₋₁₅ alcohols containing 3 EO, 5 EO, 7EO or 8 EO, C₁₂₋₁₈ alcohols containing 3 EO, 5 EO or 7 EO and mixturesthereof, such as mixtures of C₁₂₋₁₄ alcohol containing 3 EO and C₁₂₋₁₈alcohol containing 5 EO. The degrees of ethoxylation mentioned arestatistical mean values which, for a particular product, may be a wholenumber or a broken number. Other preferred nonionic surfactants are, inparticular, tallow fatty alcohols containing 11 EO, 14 EO, 25 EO, 30 EOor 40 EO. On account of the well-known pluming problem attending thespray drying of ethoxylated alcohols, which is produced by the steamvolatility of unreacted alcohol and alcohols with low degrees ofethoxylation, the ethoxylated fatty alcohols preferably used contain anaverage of at least 5 EO groups in the molecule. For the same reason,preferred alcohol ethoxylates also have a narrow homolog distribution(narrow range ethoxylates, NRE). Tallow fatty alcohols or C₁₂₋₁₈ fattyalcohols containing 5 to 25 EO, preferably mixtures of fatty alcoholscontaining 5 EO and/or 7 EO and 25 EO or mixtures of fatty alcoholscontaining 5 EO and 14 EO, are particularly preferred.

Suitable alkoxylated alcohols may also be propoxylated or bothethoxylated and propoxylated. According to the invention, however, it ispreferred to use only ethoxylated alcohols by virtue of the betterresulting product properties. The content of ethoxylated fatty alcohols,particularly tallow fatty alcohols containing 5 to 25 EO, in thegranules is in particular from 10 to 15% by weight.

In addition, alkyl glycosides corresponding to the general formulaRO(G)_(x), in which R is a primary linear or methyl-branched, moreespecially 2-methyl-branched, aliphatic radical containing 8 to 22carbon atoms and preferably 12 to 18 carbon atoms and G stands for aglycose unit containing 5 or 6 carbon atoms, preferably glucose, mayalso be used as additional nonionic surfactants. The degree ofoligomerization x, which indicates the distribution of monoglycosidesand oligoglycosides, is a number of 1 to 10 and preferably from 1.2 to1.4.

Another class of preferred nonionic surfactants, which are used eitheras sole nonionic surfactant or in combination with other surfactants,more particularly with alkoxylated fatty alcohols, are alkoxylated andpreferably ethoxylated or ethoxylated and propoxylated fatty acid alkylesters, preferably containing 1 to 4 carbon atoms in the alkyl chain,more particularly the fatty acid methyl esters described, for example,in Japanese patent application JP 58/217598 or those preferably producedby the process described in International patent applicationWO-A-90/13533.

Nonionic surfactants of the amine oxide type, for exampleN-cocoalkyl-N,N-dimethylamine oxide andN-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acidalkanolamides are also suitable nonionic surfactants. The quantity inwhich these nonionic surfactants are used is preferably no more thanthat and, more preferably, no more than half that in which theethoxylated fatty alcohols are used.

Other suitable surfactants are polyhydroxy fatty acid amidescorresponding to formula (I): ##STR1## in which R² CO is an aliphaticacyl radical containing 6 to 22 carbon atoms, R³ is hydrogen, an alkylor hydroxyalkyl radical containing 1 to 4 carbon atoms and Z! is alinear or branched polyhydroxyalkyl radical containing 3 to 10 carbonatoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides areknown substances which may typically be obtained by reductive aminationof a reducing sugar with ammonia, an alkylamine or an alkanolamine andsubsequent acylation with a fatty acid, a fatty acid alkyl ester or afatty acid chloride.

The granules preferably contain as sugar acids or salts of sugar acidspolyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid saltscontaining 4 to 6 carbon atoms, each carbon atom that does not bear acarboxyl group or keto group carrying a hydroxy group, and/orpolyhydroxydicarboxylic acids or polyhydroxydicarboxylic acid saltscontaining 4 to 6 carbon atoms and at least two hydroxy groups permolecule or mixtures of these acids and salts. Polyhydroxymonocarboxylicacids or polyhydroxymonocarboxylic acid salts containing one keto groupper molecule, preferably lactones, are formed. Preferredpolyhydroxymonocarboxylic acids or polyhydroxymonocarboxylic acid saltsare those which contain 4 to 6 carbon atoms and which carry a hydroxygroup at each carbon atom that does not bear a carboxyl group or ketogroup. Polyhydroxymonocarboxylic acids and polyhydroxymonocarboxylicacid salts containing 4 carbon atoms and 3 hydroxy groups, 5 carbonatoms and 4 hydroxy groups and 6 carbon atoms and 4 or 5 hydroxy groupsare particularly preferred. Particularly advantageous properties areexhibited by polyhydroxymonocarboxylic acids orpolyhydroxymonocarboxylic acid salts containing 6 carbon atoms and 5hydroxy groups, such as D-gluconic acid (also known as maltonic acid ordextronic acid) or salts thereof and polyhydroxymonocarboxylic acids orpolyhydroxymonocarboxylic salts containing 6 carbon atoms, 1 keto groupand 4 hydroxy groups, such as L-ascorbic acid, which is also present aslactone, and L-ascorbic acid salts. Mixtures of the acids and/or saltsmay be used, the salts preferably being the sodium or potassium salts.However, polyhydroxydicarboxylic acids or polyhydroxydicarboxylic acidsalts which contain 4 to 6 carbon atoms and which carry a hydroxy groupat each carbon atom that does not bear a carboxyl group are alsopreferred. Accordingly, particular preference is attributed topolyhydroxydicarboxylic acids and polyhydroxydicarboxylic acid saltscontaining 4 carbon atoms and 2 hydroxy groups, such as tartaric acidand tartaric acid salts, and 6 carbon atoms and 4 hydroxy groups, suchas galactaric acid (also known as mucic acid) and galactaric acid saltsand also glucaric acid (also known as saccharic acid) and glucaric acidsalts. Mixtures of the acids, the monosalts and/or the disalts may alsobe used. The salts are preferably used in the form of sodium orpotassium salts. Accordingly, particularly advantageouspolyhydroxydicarboxylic acid salts include the monosodium salts anddisodium salts and the monopotassium and dipotassium salts of tartaricacid, galactaric acid and D-glucaric acid.

The content of sugar acids and, preferably, salts of sugar acids in thespray dried granules is preferably from 0.2 to 20% by weight and, morepreferably, from 0.5 to 15% by weight. Spray-dried granules containing 1to 10% by weight and advantageously 2 to 5% by weight of gluconic acid,gluconate or mixtures thereof are particularly preferred.

The granules according to the invention may contain other ingredientstypically used in detergents or cleaning compositions. Preferredgranules, which are used either as household detergents or as acomponent of household detergents or institutional detergents,preferably contain inorganic or inorganic and organic builders.Inorganic builders include above all phosphates, more particularly theknown tripolyphosphates, and zeolite.

The finely crystalline, synthetic zeolite containing bound water used ispreferably zeolite NaA in detergent quality. However, zeolite NaX,zeolite P and mixtures of NaA, NaX and optionally P are also suitable.The zeolite may be used in the form of a spray-dried powder although itmay also be used with advantage in the form of an undried stabilizedsuspension still moist from its production. In cases where the zeoliteis used in the form of a suspension, the suspension may contain smalladditions of nonionic surfactants as stabilizers, for example 1 to 3% byweight, based on zeolite, of ethoxylated C₁₂₋₁₈ fatty alcoholscontaining 2 to 5 ethylene oxide groups, C₁₂₋₁₄ fatty alcoholscontaining 4 to 5 EO or ethoxylated isotridecanols. Suitable zeoliteshave an average particle size of less than 10 μm (volume distribution,as measured by the Coulter Counter method) and preferably contain 18 to22% by weight and, more preferably, 20 to 22% by weight of bound water.

Suitable substitutes or partial substitutes for the zeolite are layersilicates of natural and synthetic origin. Corresponding layer silicatesare known, for example, from patent applications DE-B-23 34 899, EP-A-0026 529 and DE-A-35 26 405. However, their suitability is not confinedto a particular composition or structural formula. However, smectitesand especially bentonites are preferred.

The phosphate and/or zeolite content of the spray-dried granules ispreferably from 20 to 60% by weight and, more preferably, from 20 to 50%by weight, based on water-free active substance. Small quantities of 20to 25% by weight may be used with advantage in particular whenphosphates and zeolites are used.

Useful organic builders which may be used in addition to the sugar acidsor their salts are, for example, the polycarboxylic acids preferablyused in the form of their sodium salts, such as citric acid, adipicacid, succinic acid, glutaric acid, aminocarboxylic acids,nitrilotriacetic acid (NTA), providing their use is not objectionable onecological grounds, and mixtures thereof. Preferred salts are the saltsof polycarboxylic acids, such as citric acid, adipic acid, succinicacid, glutaric acid and mixtures thereof.

Suitable polymeric polycarboxylates are, for example, the sodium saltsof polyacrylic acid or polymethacrylic acid, for example those with arelative molecular weight of 800 to 150,000 (based on acid). Suitablecopolymeric polycarboxylates are, in particular, those of acrylic acidwith methacrylic acid and those of acrylic acid or methacrylic acid withmaleic acid. Copolymers of acrylic acid with maleic acid containing 50to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acidhave proved to be particularly suitable. Their relative molecularweight, based on free acids, is generally in the range from 5,000 to200,000, preferably in the range from 10,000 to 120,000 and morepreferably in the range from 50,000 to 100,000.

The (co)polymeric polycarboxylates may be used either in the form of apowder or in the form of an aqueous solution, 20 to 55% by weightaqueous solutions being preferred.

Other suitable builders are polyacetals which may be obtained byreaction of dialdehydes with polyol carboxylic acids containing 5 to 7carbon atoms and at least 3 hydroxyl groups, for example as described inEuropean patent application EP-A-0 280 223. Preferred polyacetals areobtained from dialdehydes, such as glyoxal, glutaraldehyde,terephthalaldehyde and mixtures thereof, and from polyol carboxylicacids, such as gluconic acid and/or glucoheptonic acid.

Other suitable ingredients of the granules are water-soluble inorganicsalts, such as bicarbonates, carbonates, amorphous silicates or mixturesthereof. Alkali metal carbonate and amorphous alkali metal silicate,above all sodium silicate with a molar ratio of Na₂ O to SiO₂ of 1:1 to1:4.5 and preferably 1:2 to 1:3.5, are particularly suitable. The sodiumcarbonate content of the granules is preferably up to 20% by weight andadvantageously from 5 to 15% by weight where the granules are to be usedin the home and may be increased to a content of preferably up to 50% byweight and, more preferably, up to 45% by weight for institutionalapplications. The sodium silicate content of the granules is generallyup to 10% by weight and preferably from 2 to 8% by weight, quantities ofsilicate of at most 3% by weight being preferred for zeolite-containinggranules.

According to the teaching of earlier German patent application P 43 19578.4, alkali metal carbonates may even be replaced by sulfur-free aminoacids containing 2 to 11 carbon atoms and, optionally, another carboxyland/or amino group and/or salts thereof. According to the invention, thealkali metal carbonates are preferably partly or completely replaced byglycine or glycinate.

The other detergent ingredients which may be present in the granulesinclude redeposition inhibitors, foam inhibitors, optical brighteners,enzymes, fabric softeners, dyes and fragrances and neutral salts, suchas sulfates and chlorides in the form of their sodium or potassiumsalts.

Where the granules are used in machine washing processes, it can be ofadvantage to add conventional foam inhibitors to them. Suitable foaminhibitors are, for example, soaps of natural or synthetic origin with ahigh percentage content of C₁₈₋₂₄ fatty acids. Suitablenon-surface-active foam inhibitors are, for example, organopolysiloxanesand mixtures thereof with microfine, optionally silanized silica andalso paraffins, waxes, microcrystalline waxes and mixtures thereof withsilanized silica or bis-stearyl ethylenediamine. Mixtures of differentfoam inhibitors, for example those of silicones, paraffins or waxes, arealso used with advantage.

The neutrally reacting sodium salts of, for example,1-hydroxyethane-1,1-diphosphonate and diethylenetriamine pentamethylenephosphonate are preferably used in quantities of 0.1 to 1.5% by weightas the salts of polyphosphonic acids.

Suitable enzymes are enzymes from the class of proteases, lipases,amylases, cellulases and mixtures thereof. Enzymes obtained frombacterial strains or fungi, such as Bacillus subtilis, Bacilluslicheniformis and Streptomyces griseus, are particularly suitable.Proteases of the subtilisin type and, in particular, proteases obtainedfrom Bacillus lentus are preferably used. Enzyme mixtures, for exampleof protease and amylase or protease and lipase or protease and cellulaseor of cellulase and lipase or of protease, amylase and lipase orprotease, lipase and cellulase, but especially cellulase-containingmixtures, are of particular interest. Oxidases and peroxidases have alsoproved to be suitable in some cases. The percentage content of enzymes,enzyme mixtures or enzyme granules may be, for example, from about 0.1to 5% by weight and is preferably from 0.1 to about 2% by weight.

The function of redeposition inhibitors is to keep the soil detachedfrom the fibers suspended in the liquor and thus to preventdiscoloration. Suitable redeposition inhibitors are water-soluble,generally organic colloids, for example the water-soluble salts ofpolymeric carboxylic acids, glue, gelatine, salts of ether carboxylicacids or ether sulfonic acids of starch or of cellulose or salts ofacidic sulfuric acid esters of cellulose or starch. Water-solublepolyamides containing acidic groups are also suitable for this purpose.Other suitable redeposition inhibitors are soluble starch preparationsand other starch products than those mentioned above, for exampledegraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone may alsobe used. However, cellulose ethers, such as carboxymethyl cellulose,methyl cellulose, hydroxyalkyl cellulose, and mixed ethers, such asmethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methylcarboxymethyl cellulose and mixtures thereof, and polyvinyl pyrrolidoneare preferably used.

The granules may contain derivatives of diaminostilbene disulfonic acidor alkali metal salts thereof as optical brighteners. Suitable opticalbrighteners are, for example, salts of4,4'-bis-(2-anilino-4-morphilino-1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonicacid or compounds of similar structure which contain a diethanolaminogroup, a methylamino group, an anilino group or a 2-methoxyethylaminogroup instead of the morpholino group. Brighteners of the substituteddiphenyl styryl type, for example alkali metal salts of4,4'-bis-(2-sulfostyryl)-diphenyl,4,4'-bis-(4-chloro-3-sulfostyryl)-diphenyl or4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl, may also be present.Mixtures of the brighteners mentioned above may also be used.

In one preferred embodiment of the invention, however, the spray-driedgranules are produced without bleaching agents, bleach activators andenzymes and optionally without foam inhibitors. These standardingredients of household detergents may advantageously be subsequentlymixed with the spray-dried granules either as a raw material or in theform of a compound prepared beforehand.

In another preferred embodiment of the invention, the spray-driedgranules are used as basic granules for the production of institutionaldetergents. In this case, they may be mixed, for example, with alkalinesubstances, such as metasilicate.

The percentage content of spray-dried granules in domestic orinstitutional detergents is preferably from 40 to 90% by weight and morepreferably from 50 to 85% by weight.

The present invention also relates to a process for the production ofspray-dried granules and, more particularly, for the production of theabove-mentioned granules according to the invention which may be used inparticular as detergents or cleaning compositions or as a componenttherefor. Production is carried out via the spray drying of a slurrycontaining less than 35% by weight of water. The viscosity of the slurryunder the operating conditions should be no more than 15,000 mPas inorder to ensure safe processing of the slurry in the tower. According tothe invention, it is possible and therefore preferred further to reducethe water content of the slurry. Thus, water contents of at most 30% byweight, preferably from 15 to 30% by weight and more preferably from 15to 25% by weight are preferred. Another preferred embodiment of theinvention is characterized by the use of slurries which have a viscosityunder the operating conditions of less than 12,000 mPas and, moreparticularly, in the range from 5,000 to 10,000 mPas. Correspondingslurries are obtained when they contain polyhydroxymonocarboxylic acidsaccording to the invention or salts thereof, polyhydroxydicarboxylicacids or salts thereof or mixtures of these mono- and/or di-compounds inthe quantities indicated. However, polyhydroxymonocarboxylic acids orpolyhydroxymonocarboxylic acid salts are preferably used, gluconic acidand advantageously gluconate being particularly preferred. The sugaracids and, in particular, the salts of the sugar acids may beincorporated in the slurry in solid form or in the form of an aqueoussolution, for example in the form of a 60 to 80% by weight aqueoussolution.

The apparent densities of the granules thus produced may vary withinwide limits. The expert knows those parameter changes in the spraydrying process which lead to lighter granules and those which lead toheavier granules. For example, it is possible to produce granules withan apparent density of 550 g/l and higher. However, apparent densitiesof 700 to 1000 g/l and, more particularly, of the order of 750 to 800g/l are preferably established in this spray-drying process. Theseapparent densities can readily be established in conventional spraydrying towers.

This process not only solves the problems of increasing the performancelevels and capacities of the spray-drying towers for the same energyconsumption (increases in performance of 20% and higher are possible)while at the same time ensuring the processability of highlyconcentrated slurries (concentration by 10% or more in relation to theprior art is possible), a higher degree of phosphate retention is alsoachieved in the spray drying of tripolyphosphate-containing granules.This can be explained, for example, by the fact that the reduction inthe slurry viscosities also enables the tower entry temperatures to bereduced (lower energy consumption), thereby suppressing decomposition ofthe tripolyphosphate. This in turn means that smaller quantities ofphosphates can be used through the increased degree of retention withoutany deterioration in the primary washing performance.

However, another significant advantage is the increase in the apparentdensity of the spray-dried granules so that further compacting measures(for example compacting granulation) are largely unnecessary. Theadvantage of this is that uniform free-flowing, heavy but low-dustgranules are obtained. The possibility of reducing the tower entrytemperatures enables the user to incorporate higher percentages ofethoxylated fatty alcohols in the spray-dried granules because thenotorious problem of pluming (plume of smoke caused by escaping fattyalcohol ethoxylates) is also reduced by the lower temperatures.

EXAMPLES Comparison Example C1

Granules C1 with the composition shown below were produced by spraydrying:

    ______________________________________                                        Tallow fatty alcohol · 5 EO                                                               7% by weight                                             Tallow fatty alcohol · 14 EO                                                              7% by weight                                             Sodium carbonate     41% by weight                                            Sodium tripolyphosphate                                                                            31.5% by weight                                          Sodium silicate (Na.sub.2 O:SiO.sub.2 1:3.0)                                                       4.5% by weight                                           Carboxymethyl cellulose (CMC) and                                                                  0.9% by weight                                           methyl cellulose (MC)                                                         Optical brightener   0.2% by weight                                           1-Hydroxyethane-1,1-diphosphonate (HEDP)                                                           0.35% by weight                                          Water                balance to 100% by weight                                ______________________________________                                    

In Comparison Example C1, the slurry concentration was 69.3% by weightand the viscosity under operating conditions was 7500 mPas. The apparentdensity was 567 g/l.

Example M1/1

The Comparison Example was repeated; the operating conditions of thespray drying tower were established as in C1 with no changes and 2% byweight, based on the spray-dried granules, of sodium gluconate in solidform (100% by weight) were used instead of sodium carbonate. The slurryconcentration was still 69.3% by weight and the viscosity underoperating conditions was 5300 mPas. The apparent density of thespray-dried granules M1/1 was 631 g/l.

Example 2

Comparison granules C2 and granules M2/1 to M2/6 according the invention

Comparison granules C2 with the same composition as C1 above wereprepared by spray drying of a 69.8% by weight slurry. The viscosity ofthe slurry under operating conditions was again 7500 mPas and theapparent density 570 g/l.

M2/1

Repetition of the Example with 0.7% by weight, based on the spray-driedgranules, of sodium gluconate instead of sodium carbonate. The gluconatewas incorporated in the slurry in the form of a 70% by weight aqueoussolution. The viscosity of the slurry under operating conditions was6300 mPas. The apparent density of the spray-dried granules was 590 g/l.

M2/2

Repetition of the Example with 1.4% by weight, based on the spray-driedgranules, of sodium gluconate instead of sodium carbonate. The gluconatewas incorporated in the slurry in the form of a 70% by weight aqueoussolution. The viscosity of the slurry under operating conditions was5300 mPas. The apparent density of the spray-dried granules was 617 g/l.

M2/3

Repetition of the Example with 2.8% by weight, based on the spray-driedgranules, of sodium gluconate instead of sodium carbonate. The gluconatewas incorporated in the slurry in the form of a 70% by weight aqueoussolution. The viscosity of the slurry under operating conditions was4200 mPas. The apparent density of the spray-dried granules was 639 g/l.

M2/4

Repetition of the Example with a 70.1% by weight slurry and 1% byweight, based on the spray-dried granules, of sodium gluconate insteadof sodium carbonate. The gluconate was incorporated in the slurry insolid form (100% by weight). The viscosity of the slurry under operatingconditions was 6500 mPas. The spray-dried granules had an apparentdensity of 643 g/l.

M2/5

Repetition of the Example with a 70.4% by weight slurry and 2% byweight, based on the spray-dried granules, of sodium gluconate insteadof sodium carbonate. The gluconate was incorporated in the slurry insolid form (100% by weight). The viscosity of the slurry under operatingconditions was 5300 mPas. The spray-dried granules had an apparentdensity of 657 g/l.

M2/6

Repetition of the Example with a 71.0% by weight slurry and 4% byweight, based on the spray-dried granules, of sodium gluconate insteadof sodium carbonate. The gluconate was incorporated in the slurry insolid form (100% by weight). The viscosity of the slurry under operatingconditions was 5000 mPas. The spray-dried granules had an apparentdensity of 682 g/l.

Example 3

Comparison granules C3 and granules M3/1 to M3/2 according to theinvention

Comparison granules C3 with the same composition as C1 and C2 wereproduced by spray drying a 72.9% by weight slurry. However, theviscosity under operating conditions was well above 20,000 mPas.

M3/1

Repetition of the Example with a 73.4% by weight slurry and 2% byweight, based on the spray-dried granules, of sodium gluconate insteadof sodium carbonate. The gluconate was incorporated in the slurry insolid form (100% by weight). The viscosity of the slurry under operatingconditions was 8000 mPas. The spray-dried granules had an apparentdensity of 706 g/l.

M3/2

Repetition of the Example with a 74.0% by weight slurry and 4% byweight, based on the spray-dried granules, of sodium gluconate insteadof sodium carbonate. The gluconate was incorporated in the slurry insolid form (100% by weight). The viscosity of the slurry under operatingconditions was 7000 mPas. The spray-dried granules had an apparentdensity of 742 g/l.

Example 4

Comparison granules C4 and granules M4/1 to M4/4 according to theinvention

Comparison granules C4 with the same composition as C1 to C3 were to beproduced by spray drying of a 74.6% by weight slurry. The viscosityunder operating conditions was not measurable and the slurry could notbe stirred.

M4/1

Repetition of the Example with a 75.1% by weight slurry and 2% byweight, based on the spray-dried granules, of sodium gluconate insteadof sodium carbonate. The gluconate was incorporated in the slurry insolid form (100% by weight). The viscosity of the slurry under operatingconditions was 11,500 mPas. The spray-dried granules had an apparentdensity of 758 g/l.

M4/2

Repetition of the Example with a 75.6% by weight slurry and 4% byweight, based on the spray-dried granules, of sodium gluconate insteadof sodium carbonate. The gluconate was incorporated in the slurry insolid form (100% by weight). The viscosity of the slurry under operatingconditions was 9700 mPas. The spray-dried granules had an apparentdensity of 769 g/l.

M4/3

2% by weight, based on the spray-dried granules, of sodium gluconatewere used instead of sodium carbonate. However, the concentration of theslurry was 75.9% by weight and the viscosity under operating conditionswas 12,000 mPas. The spray-dried granules had an apparent density of 762g/l.

M4/4

3% by weight, based on the spray-dried granules, of sodium gluconatewere used instead of sodium carbonate. The concentration of the slurrywas 75.9% by weight as in M4/3 although its viscosity under operatingconditions was only 10,000 mPas. The spray-dried granules had anapparent density of 749 g/l.

The apparent densities of the individual products according to theinvention could be further increased by routine changes familiar to theexpert in the conditions prevailing in the spray drying tower.

What is claimed is:
 1. Spray-dried granules useful as detergents,cleaning compositions or as a component therefor containing anionicsurfactants in an amount of less than 1% by weight, soap in an amount ofless than 0.2% by weight, 1 to 30% by weight of nonionic surfactants,0.2% to 20% by weight of sugar acids or salts of sugar acids, and thebalance to 100% by weight of inorganic or organic builders, redepositioninhibitors, foam inhibitors, optical brighteners, enzymes, fabricsofteners, dyes, fragrances and neutral salts, based on the weight ofsaid granules, said granules having an apparent density of at east 550g/l.
 2. Granules as in claim 1 having an apparent density of 700 to 1000g/l.
 3. Granules as in claim 1 containing 2 to 25% by weight of nonionicsurfactants.
 4. Granules as in claim 1 wherein said sugar acids or saltsof said sugar acids are selected from the group consisting ofpolyhydroxymonocarboxylic acids having 4 to 6 carbon atoms or saltsthereof, wherein each carbon atom that does not bear a carboxyl group orketo group carries a hydroxy group, and polyhydroxydicarboxylic acidscontaining 4 to 6 carbon atoms and at least 2 hydroxy groups permolecule, or salts thereof.
 5. Granules as in claim 1 containing 0.5 to15% by weight of gluconic acid, gluconate or mixtures thereof.
 6. Agranular household detergent composition containing 40% to 90% by weightof the spray-dried granules of claim 1, and the balance to 100% byweight of conventional household detergent composition ingredients.
 7. Agranular institutional detergent composition containing 40 to 90% byweight of the spray-dried granules of claim 1, and the balance to 100%by weight of conventional institutional detergent compositioningredients.
 8. The process of producing spray-dried granules useful asdetergents, cleaning compositions, or as a component therefor,comprising preparing a slurry containing 0.2% to 20% by weight of sugaracids or salts thereof and the balance being detergent components, saidslurry containing less than 35% by weight of water, less than 1% byweight of anionic surfactants, and less than 0.2% by weight of soap andhaving a viscosity of less than 15,000 mPas under spray-dryingconditions, and spray-drying said slurry.
 9. A process as in claim 8wherein said slurry has a water content of at most 30% by weight.
 10. Aprocess as in claim 8 wherein said slurry has a viscosity of less than12,000 mPas.
 11. A process as claimed in claim 8 wherein said sugaracids or salts thereof are selected from the group consisting ofpolyhydroxymonocarboxylic acids containing 4 to 6 carbon atoms and atleast 3 hydroxy groups per molecule, salts thereof, and mixturesthereof, polyhydroxydicarboxylic acids containing 4 to 6 carbon atomsand at least 2 hydroxy groups per molecule, salts thereof, and mixturesthereof.
 12. A process as in claim 8 wherein said sugar acids or saltsthereof comprise polyhydroxymonocarboxylic acids orpolyhydroxymonocarboxylic acid salts containing 4 to 6 carbon atoms,each carbon a tom that does not bear a carboxyl group or keto groupcarries a hydroxy group.
 13. A process as in claim 8 wherein said slurrycontains 0.5 to 15% by weight of gluconic acid, gluconate or mixturesthereof, based on the weight of said spray-dried granules.
 14. A processas in claim 8 wherein said granules have an apparent density of 700 to1000 g/l.
 15. The product of claim
 8. 16. The product of claim
 9. 17.The product of claim
 10. 18. The product of claim
 11. 19. The product ofclaim
 12. 20. The product of claim 13.